Composition of matter comprising



Reiosuecl May 12, 1936 UNITED STATES; PATENT OFFICE COMPOSITION OFMATTER COMPRISING RESIN ESTERS arry M. Weber, Newton, Mass., assignor toEllis-Foster Company, a corporation or New Jersey No Drawing.

Original No.'1,722,776,' dated July 30, 1929, Serial No. 595,862,October 20, 1922. Application for reissue, March 20, 1936, Serial i 16Claims.

This invention relates to compositions comprising artificial resins andcellulose esters and relates especially'to compositions containingartificial resins derived by reaction between organic acids andpolyhydric alcohols.

In the present invention it is an object to provide a composition whichhas qualities of toughness, flexibility, extensibility and the likeenabling tough spirit varnishes to be prepared and also to permit of theemployment of the toughened material in the production of films, plasticcompositions, molded articles and the like.

Various resins such as those commonly used inthe varnish industry, forexample,'ordinary rosin, contain from small to considerable amounts ofresin acids which combine with, for example,

glycerine on heating and the esters obtained, be-

ing more nearly neutral substances, find extensive use in the varnishfield. Ordinary rosin ester,

. having limited solubilities. If, however, a nonresinous organic acidsuch as phthalic acid is allowed to esterify with glycerine inconjunctionwith rosin, a valuable product is obtained which may betermed a rosin phthalic ester of glycerol or. a rosin phthalic glycerideresin. As is well known nitrocellulose is incompatible with a great manysubstances. Most of the resins which dissolve in solvents fornitrocellulose are not miscible with the latter and when a solutioncontaining any substantial amount of resin and nitrocellulose is allowedto dry the solid components segregate and a worthless mass results. 01course nitrocellulose will assimilate small quantities of resins withoutgreatly affecting its toughness and flexibility but no substantialamounts may be added without impairing the.

qualities for which nitrocellulose is employed.

I have found that the rosin phthalic glyceride resin will dissolve, mixor blend with nitrocellulose and apparently in almost any proportion.Hence it becomes possible to introduce nitrocellulose, pyroxylin,soluble cotton, celluloid such for example as scrap celluloid and usedmoving picture film to serve as a toughening agent. The addition of 10to 20 per cent of such nitrocellulose compounds greatly improves thetoughness of the resin and still' larger quantities may be used whenadditional toughness isdesired. For

55 amounts of nitrocellulose suchas 40' or per cent or ester gum as itis called, is a brittle substance example by the addition of 25 to 30per cent of serve to increase the filming properties and the toughnessof the resulting films. One may proceed further with additions ofnitrocellulose so that the latter component predominates and the resinmay be present in amounts of 40, 30, 20, 10' per cent etc. as may bedesired when films of great toughness or special plastic products arerequired. The rosin phthalic glyceride resin as ordinarily prepared isnot as light in color as good quality nitrocellulose and the tintresulting from the presence of a large proportion of the rosin phthalicglyceride resin is objectionable for some purposes, in which case thenitrocellulose may predominate.

There are many uses for such a material as for example varnishes,lacquers, japans, paints, substitutesfor hard rubber and various othermolded plastic products, films for various purposes as for example theWindshields of automobiles and other purposes for which films of thisgeneral 20 character may be utilized appropriately.

The rosinphthalic glyceride resin in a form readily soluble in acetoneand the customary solvents of nitrocellulose is of itself more readilyaffected by water than nitrocellulose and the latter besides having atoughening and strengthening efiect also co-operates with the rosinphthalic glyceride resin to increase the resistance to water, so thatspotting or disintegration of the surface through the action of water isnot as likely to 3 occur. On the other'hand the presence of asubstantial or predominating amount of the rosin -phthalic glycerideresin apparently reduces the inflammability and explosibility ofnitrocellulose to a considerable extent which of course is ad- 35vantageous for many purposes. In addition to rosin I may of course useother appropriate resins such as 'copal resins whose esters are of acharacter adapted to admix with nitrocellulose or other cellulose estersor ethers. 40 Thus I may prepare a resin phthalic glyceride resin fromcongo or other copal resin, phthalic acid and glycerine preferably withthe addition of some rosin to serve as a fluxing agent. While a I havementioned phthalic acid particularly it 45 should be understood that Iembrace within the scope of this application various other organic acidscapable of esterifying with glycerine to give complexes soluble in theusual solvents of the nitrocellulose industry, e. g. methyl, ethyl andso amyl alcohol, ethyl acetate, amyl acetate and in mixtures of suchsolvents with hydrocarbon diluents such as benzol or toluol. The acidspreferably employed are polybasic aliphatic acids such as maleic,fumaric, succinic, malic, citric, tartaric to make the resin phthalicglyceride resin capable of blending with nitrocellulose whereby thelatter may be employed as a toughening agent for the resin phthalicglyceride resin, or on the other hand the latter may be used as a meansof modifying the character of nitrocellulose or cheapening it. Theaddition of softening agents such as castor oil, camphor, triphenyl ortricresyl phosphate, diethyl phthalate and the like is not excludedalthough many useful compositions may be prepared without the additionof such softening agents. Scrap celluloid containing camphor or camphorsubstitute forms a cheap and readily available toughening agent for theresinous complex.

When a solution of nitrocellulose in for example acetone without anywater eliminant such as insel oil or amyl acetate is allowed to dry awhite, opaque film usually forms. When a substantial proportion of therosin phthalic glyceride resin of this invention is present no suchwhitening and opacity is observed a clear film being formed as though aspecial water eliminant had been added.

To illustrate the toughening effect that the addition of smallquantities of nitrocellulose has on coatings prepared from solutions ofthe resin phthalic glyceride resin the following examples are cited.

5 parts of soluble cotton mixed with 95, parts of the rosin phthalicglyceride resin were dissolved in acetone and the solution was allowedto flow and allowed to harden for aperiod of 24 hours. A similar coatingwas prepared from a solution of the rosin phthalic glyceride resin andcomparative tests made on the resulting coatings. I found that theaddition of this small amount of nitro-' cellulose toughened theresulting coating considerably. The rosin phthalic glyceride resincoating could readily bescratched with a sharp cornered flake of shellacwhile the coating containing the nitrocellulose was not scratched.Coatings containing 10 per cent, 20 per cent, 33% per cent and 50 percent nitrocellulose or soluble cotton behaved in a similar manner. Allof the coatings were clear and transparent, the color varyingproportionally with the amount of nitrocellulose incorporated-with theresin. The coatings' containing 20 per cent and more of nitrocellulosecould be stripped from the glass plates intact.

The rosin phthalic glycerlde resin is miscible with nitrocellulose inall proportions-and as an illustration the following example is given.

5 parts oi. rosin phthallc glycerlde resin and parts of soluble cottonwere dissolved in 2000 parts or acetone. A fllm prepared by flowing theoohrtionona-glass plateand allowingthefllm todrywasalightlymore'brlttlethan afllmpre- Daredmnnaflnble cotton alone. Theadditlm.

otmernrtdcastorolltotheaolutionhopever runedlenl an defect and thecoating obtained "mammalian-amt. Assnel-pledl'nnflrwhlchilllaliftorcoltannihilation-misused. 25

- in a solution consisting of a mixture of parts tained and thiscondition usually presents itself on a glass plate. The coating was thendried corporated with nitrocellulose.

4. A composition of matter comprising a glycwith nitrocellulose.

with nitrocellulose and a softening agent.

- 9. A composition of matter comprising glyc- .addmnunthegroupconsistingof parts of rosin phthalic glyceride resin and 50 parts 0! scrap motionpicture film was dissolved of acetone and 50 parts or benzol. Thesolution prepared in this manner was quite viscous but would flowreadily at room temperature. A coating obtained by the use 01' thissolution was tough and transparent and light yellow in color.

As another example a solution of 90 parts of rosin phthalic glycerideresin, 10 parts of scrap motion picture filmwas dissolved in 14 parts ofacetone. A coating obtained by the use oi this solution was tough,transparent and resistant to the action or water.

The condition of compatibility may be ascribed to'a state of solidsolution, that is the nitrocellulose and the synthetic resin dissolve inone another-or are so intimately mixed that a clear, transparent, toughsolid results. With an incompatible resin, a turbid, opaque, weak solidis obat the point where most of the solvent has evaporated. Such solidsolution may form in the first instance when using a resin which is notcompatible with nitrocellulose but on standing or through unknowncauses, changes may occur due to separation or expulsion of onecomponent from the immediate zone of the other and substantialdeterioration result.

By the term resin acid as used in the claims, it is intended to coveracids which. are normal constituents of resins. I

What I claim is: I

1. A composition of matter comprising a rosin phthalic glyceride resinsoluble in nitrocellulose solvents, admixed with nitrocellulose.

2. A composition of matter'comprising a rosin 3. A composition of mattercomprising a glycerol ester of a resin and organic carboxylic acidselected from the group consisting of phthalic, malelc, fumaric, malicand succinic acids, in-

erol ester oi a resin and organic carboxylic acid selected from thegroup consisting of phthalic, maleic, fumaric, malic and succinic acids,incorporated with a cellulose ester.

5. A composition of matter comprising a polyhydric alcohol ester of. aresin and organic car-' boxylic acid selected from the group consistingof phthalic, maleic, Iumaric, malic and succinic acids, incorporatedwith nitrocellulose.

6. A composition of matter comprising a glycerol ester of aresin andphthalic acldincorporated I. A composition of matter comprising aglycwith nitrocellulose.

8. A composition of matter comprising a glycerol ester ofrosin andphthalic acid incorporated erolesterofrosinandphthalicacidincorporatedwithaagentcomprising nitrocellulose.

10. A of matter comprising the glycerol ate: 1! a resin and an organicdihaslc acid with I'hth B incorporated a agmtnih'ocellulose.

ILA varnkh .01 a solutlon of a glycadsta-dareslnandorganlc carboxylicacids, incorporated with nitrocellulose.

phthalic-glyceride resin which yields phthaiic phthalic, maleic,iumaric, malic and succinic 15. A composition 01' matter comprising aglycerol ester of rosin and phthalic acid incorporated with a tougheningagent containing nitrocellulose.

16. A composition 0! matter comprising the p y ydric alcoholrester of aresin and organic carboxylic acid selected from the group consist.- ing01' phthalic, maleic, iuznaric, malic and sucacid upon hydrolysis,admixed with nitrocellulose. cinic acids with which is ineo p rated atou8 eni4. A plastic composition containing aresining agent containingnitrocellulose.- dibasic, organic acid-glyceride resin, which yields aan organic, dibasic acid upon hydrolysis, admixed with nitrocellulose. 4v v 12. A plastic substance comprising a glycerol ester oi a resin andan organic dibasic acid incorporated with nitrocellulose.

13. A plastic composition containing a resin- 7 HARRY M. wanna.

